Polyester Quaternary Ammonium Salts

ABSTRACT

The invention relates to polyester quaternary ammonium salts, including amine, amide, and ester salts, processes for making them, and their use as additives, including their use in fuels, such as diesel fuel and fuel oils. The invention particularly relates to the use of polyester quaternary ammonium salts as detergents in fuels and the methods of making them.

FIELD OF THE INVENTION

The invention relates to polyester quaternary ammonium salts, includingamine, amide, and ester salts, processes for making them, and their useas additives, including their use in fuels, such as diesel fuel and fueloils. The invention particularly relates to the use of polyesterquaternary ammonium salts as detergents in fuels and the methods ofmaking them.

BACKGROUND OF THE INVENTION

Hydrocarbon fuels generally contain numerous deposit-forming substances.When used in internal combustion engines (ICEs), deposits tend to formon and around constricted areas of the engine which are in contact withthe fuel. In automobile engines deposits can build up on engine intakevalves leading to progressive restriction of the gaseous fuel mixtureflow into the combustion chamber and to valve sticking. There are twogeneral types of inlet valve deposits, heavy deposits and thin deposits.These different types of deposits affect the performance of the fuel andthe engine in slightly different ways. Heavy deposits are carbonaceousand oily in appearance. They cause flow restriction past the valves,which in turn reduces the maximum power of the engine, decreasing fueleconomy and increasing emissions. Thin deposits tend to cause problemson starting the engine and increasing emissions.

As engines become more sensitive to deposits, it has become commonpractice to incorporate a detergent in the fuel composition for thepurposes of inhibiting the formation, and facilitating the removal, ofengine deposits, thereby improving engine performance and emissions.

It is known to use certain polyisobutylsuccinimide-derived quaternizedPIB/amine and/or amide dispersants/detergents as additives in fuelcompositions. Polyisobutylsuccinimides may also be described aspolyisobutylene succinimides. These quaternized dispersants/detergentsare derived from traditional PIB/amine and/or amide fuel additivecompounds that have pendant tertiary amine sites which can be alkylated,i.e. quaternized, by a quaternizing agent, such as propylene oxide.Examples of these additives are disclosed in U.S. patent application US2008/0307698.

However there is a need for additives that provide the benefitsdescribed above while also exhibiting improved viscosity profiles andmaterial handling properties. Such improvements would allow for the useof less diluent materials in the concentrates and additive packagesgenerally used in the commercial products that contain these types offuel additives, and so in the final fuels as well. Less diluent would berequired if the viscosity profiles and material handling propertiesallowed for additive-containing compositions to be transferred andhandled (i.e. pumped, poured, mixed, etc) without having to heat thematerial more than typical and/or without the need of specialized highviscosity equipment. Improved viscosity profiles and material handlingproperties would allow for reduced use of diluents, saving cost,reducing waste and so and improving the environmental impact of thematerials. This would also allow the use of more concentrated additivepackages and intermediate compositions, which can be transported moreefficiently, again reducing costs and environmental impact.

SUMMARY OF THE INVENTION

The present invention deals with a new class of detergents which offersignificant improvements over traditional PIB/amine detergents,including polyisobutylsuccinimide-derived quaternized detergents. A newclass of polyester quaternized salts have now been discovered. Thesepolyester quaternized salts have polyester-based hydrocarbyl groups andprovide improved viscosity profiles and material handling propertiescompared to polyisobutylsuccinimide-derived quaternized detergents andrelated materials. The polyester quaternized salts of the inventionprovide equivalent detergency and thermal stability performance as otherquaternized detergents but also provide the improved viscosity profilesand material handling properties described above

The present invention provides a composition containing a quaternizedpolyester salt derived from the reaction of a polyester that contains atertiary amino group and a quaternizing agent suitable for convertingthe tertiary amino group to a quaternary nitrogen. The quaternizingagent may be a dialkyl sulfate, a benzyl halide, a hydrocarbylsubstituted carbonate, a hydrocarbyl epoxide, or some combinationthereof. Any of the quaternizing agents described, particularly thehydrocarbyl epoxide, may be used in combination with an acid, forexample acetic acid.

The invention provides for quaternized polyester salts where thepolyester used in their preparation is itself the reaction product of afatty carboxylic acid containing at least one hydroxyl group and acompound having an oxygen or nitrogen atom capable of condensing withsaid acid and further having a tertiary amino group. The inventionfurther provides for the polyester reactant to be a polyester amidecontaining a tertiary amino group.

The invention further provides for fuel compositions that include thequaternized polyester salts described herein and a fuel which is liquidat room temperature. Additional fuel additives may also be present.

The invention provides for methods of fueling an internal combustionengine comprising the steps of supplying to the engine a fuel which isliquid at room temperature and a composition comprising one or more ofthe quaternized polyester salts described herein.

The invention also provides for a process of making a quaternaryammonium salt detergent comprising the steps of reacting (a) a polyestercontaining a tertiary amino group; and (b) a quaternizing agent suitablefor converting the tertiary amino group to a quaternary nitrogen. Thequaternizing agent may be selected from the group consisting of dialkylsulfates, benzyl halides, hydrocarbyl substituted carbonates;hydrocarbyl epoxides in combination with an acid or mixtures thereof.The described process results in the quaternized dispersants describedherein.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

The Polyester Quaternary Ammonium Salt Detergent

The polyester quaternary salts detergents of the invention includequaternized polyester amine, amide, and ester salts. The additives mayalso be described as quaternary polyester salts. The additives of theinvention may be described as the reaction product of: a polyestercontaining a tertiary amino group; and a quaternizing agent suitable forconverting the tertiary amino group to a quaternary nitrogen. Thequaternizing agent may be selected from the group consisting of dialkylsulfates, benzyl halides, hydrocarbyl substituted carbonates;hydrocarbyl epoxides in combination with an acid or mixtures thereof

a. The Non-Quaternized Polyester

The polyester containing a tertiary amino group used in the preparationof the additives of the invention may also be described as anon-quaternized polyester containing a tertiary amino group.

In some embodiments the polyester is the reaction product of a fattycarboxylic acid containing at least one hydroxyl group and a compoundhaving an oxygen or nitrogen atom capable of condensing with said acidand further having a tertiary amino group. Suitable fatty carboxylicacids that may used in the preparation of the polyesters described abovemay be represented by the formula:

where R¹ is a hydrogen or a hydrocarbyl group containing from 1 to 20carbon atoms and R² is a hydrocarbylene group containing from 1 to 20carbon atoms. In some embodiments R¹ contains from 1 to 12, 2 to 10, 4to 8 or even 6 carbon atoms, and R² contains from 2 to 16, 6 to 14, 8 to12, or even 10 carbon atoms.

In some embodiments the fatty carboxylic acid used in the preparation ofthe polyester is 12-hydroxystearic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 5-hydroxy dodecanoic acid, 5-hydroxy decanoic acid,4-hydroxy decanoic acid, 10-hydroxy undecanoic acid, or combinationsthereof.

In some embodiments the compound having an oxygen or nitrogen atomcapable of condensing with said acid and further having a tertiary aminogroup is represented by the formula:

where R³ is a hydrocarbyl group containing from 1 to 10 carbon atoms; R⁴is a hydrocarbyl group containing from 1 to 10 carbon atoms; R⁵ is ahydrocarbylene group containing from 1 to 20 carbon atoms; and X¹ is 0or NR⁶ where R⁶ is a hydrogen or a hydrocarbyl group containing from 1to 10 carbon atoms. In some embodiments R³ contains from 1 to 6, 1 to 2,or even 1 carbon atom, R⁴ contains from 1 to 6, 1 to 2, or even 1 carbonatom, R⁵ contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R⁶contains from 1 to 8, or 1 to 4 carbon atoms. In some of theseembodiments, formula (II) becomes:

where the various definitions provided above still apply.

Examples of nitrogen or oxygen containing compounds capable ofcondensing with the acylating agents, which also have a tertiary aminogroup, or compounds that can be alkylated into such compounds, includebut are not limited to: 1-aminopiperidine, 1-(2-aminoethyl)piperidine ,1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine,4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)pyrrolidine,2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine,N,N-dimethylethylenediamine, N,N-dibutylethylenediamine,N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane,N,N,N′-trimethylethylenediamine, N,N-dimethyl-N′-ethylethylenediamine,N,N-diethyl-N′-methylethylenediamine, N,N,N′-triethylethylenediamine,3-dimethyl aminopropyl amine, 3-diethylaminopropylamine,3-dibutylaminopropylamine, N,N,N′-trimethyl-1,3-propanediamine,N,N,2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane,N,N,N′,N′-tetraethyldiethylenetriamine,3,3′-diamino-N-methyldipropylamine,3,3′-iminobis(N,N-dimethylpropylamine), or combinations thereof. In suchembodiments, the resulting additive includes a quaternary ammonium amidesalt, that is a detergent containing an amide group and a quaternaryammonium salt.

The nitrogen or oxygen containing compounds may further includeaminoalkyl substituted heterocyclic compounds such as1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine.

Another type of nitrogen or oxygen containing compounds capable ofcondensing with the acylating agent and having a tertiary amino group,in some embodiments after further alkylation, include alkanolaminesincluding but not limited to triethanolamine, N,N-dimethylaminopropanol,N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine,1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol,N-ethyldiethanolamine, N-methyldiethanol amine, N-butyldiethanolamine,N,N-diethylaminoethanol, N,N-dimethylaminoethanol,2-dimethylamino-2-methyl-1-propanol. In embodiments where alkanolaminesand/or similar materials are used, the resulting additive includes aquaternary ammonium ester salt, that is a detergent containing an estergroup and a quaternary ammonium salt.

In one embodiment the nitrogen or oxygen containing compound istriisopropanolamine, 1-[2-hydroxyethyl]piperidine,2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine,N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylamino ethanol,N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, orcombinations thereof.

In some embodiments the compound having an oxygen or nitrogen atomcapable of condensing with said acid and further having a tertiary aminogroup comprises N,N-diethylethylenediamine, N,N-dimethylethylenediamine,N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane,N,N-diethyl-1,3-diaminopropane, N,N-dimethylaminoethanol,N,N-diethylaminoethanol, or combinations thereof.

The quaternized polyester salt can be a quaternized polyester amidesalt. In such embodiments the polyester containing a tertiary aminogroup used to prepare the quaternized polyester salt is a polyesteramide containing a tertiary amino group. In some of these embodimentsthe amine or amino alcohol is reacted with a monomer and then theresulting material is polymerized with additional monomer, resulting inthe desired polyester amide which may then be quaternized.

In some embodiments the quaternized polyester salt includes an cationrepresented by the following formula:

where R¹ is a hydrogen or a hydrocarbyl group containing from 1 to 20carbon atoms and R² is a hydrocarbylene group containing from 1 to 20carbon atoms; R³ is a hydrocarbyl group containing from 1 to 10 carbonatoms; R⁴ is a hydrocarbyl group containing from 1 to 10 carbon atoms;R⁵ is a hydrocarbylene group containing from 1 to 20 carbon atoms; R⁶ isa hydrogen or a hydrocarbyl group containing from 1 to 10 carbon atoms;n is a number from 1 to 20 or from 1 to 10; R⁷ is hydrogen, ahydrocarbonyl group containing from 1 to 22 carbon atoms, or ahydrocarbyl group containing from 1 to 22 carbon atoms; and X² is agroup derived from the quaternizing agent. In some embodiments R⁶ ishydrogen.

As above, in some embodiments R¹ contains from 1 to 12, 2 to 10, 4 to 8or even 6 carbon atoms, and R² contains from 1 or even 2 to 16, 6 to 14,8 to 12, or even 10 carbon atoms, R³ contains from 1 to 6, 1 to 2, oreven 1 carbon atom, R⁴ contains from 1 to 6, 1 to 2, or even 1 carbonatom, R⁵ contains from 2 to 12, 2 to 8 or even 3 carbon atoms, and R⁶contains from 1 to 8, or 1 to 4 carbon atoms. In any of theseembodiments n may be from 2 to 9, or 3 to 7, and R⁷ may contain from 6to 22, or 8 to 20 carbon atoms. R⁷ may be an acyl group.

In these embodiments the quaternized polyester salt is essentiallycapped with a C1-22, or a C8-20, fatty acid. Examples of suitable acidsinclude oleic acid, palmitic acid, stearic acid, erucic acid, lauricacid, 2-ethylhexanoic acid, 9,11-linoleic acid, 9,12-linoleic acid,9,12,15-linolenic acid, abietic acid, or combinations thereof.

The number average molecular weight (Mn) of the quaternized polyestersalts of the invention may be from 500 to 3000, or from 700 to 2500.

The polyester useful in the present invention can be obtained by heatingone or more hydroxycarboxylic acids or a mixture of thehydroxycarboxylic acid and a carboxylic acid, optionally in the presenceof an esterification catalyst. The hydroxycarboxylic acids can have theformula HO—X—COOH wherein X is a divalent saturated or unsaturatedaliphatic radical containing at least 8 carbon atoms and in which thereare at least 4 carbon atoms between the hydroxy and carboxylic acidgroups, or from a mixture of such a hydroxycarboxylic acid and acarboxylic acid which is free from hydroxy groups. This reaction can becarried out at a temperature in the region of 160 C to 200 C, until thedesired molecular weight has been obtained. The course of theesterification can be followed by measuring the acid value of theproduct, with the desired polyester, in some embodiments, having an acidvalue in the range of 10 to 100 mg KOH/g or in the range of 20 to 50 mgKOH/g. The indicated acid value range of 10 to 100 mg KOH/g isequivalent to a number average molecular weight range of 5600 to 560.The water formed in the esterification reaction can be removed from thereaction medium, and this can be conveniently done by passing a streamof nitrogen over the reaction mixture or, by carrying out the reactionin the presence of a solvent, such as toluene or xylene, and distillingoff the water as it is formed.

The resulting polyester can then be isolated in conventional manner;however, when the reaction is carried out in the presence of an organicsolvent whose presence would not be harmful in the subsequentapplication, the resulting solution of the polyester can be used.

In the said hydroxycarboxylic acids the radical represented by X maycontain from 12 to 20 carbon atoms, optionally where there are between 8and 14 carbon atoms between the carboxylic acid and hydroxy groups. Insome embodiments the hydroxy group is a secondary hydroxy group.

Specific examples of such hydroxycarboxylic acids include ricinoleicacid, a mixture of 9- and 10-hydroxystearic acids (obtained bysulphation of oleic acid followed by hydrolysis), and 12-hydroxystearicacid, and especially the commercially available hydrogenated castor oilfatty acid which contains in addition to 12-hydroxystearic acid minoramounts of stearic acid and palmitic acid.

The carboxylic acids which can be used in conjunction with thehydroxycarboxylic acids to obtain these polyesters are preferablycarboxylic acids of saturated or unsaturated aliphatic compounds,particularly alkyl and alkenyl carboxylic acids containing a chain offrom 8 to 20 carbon atoms. As examples of such acids there may bementioned lauric acid, palmitic acid, stearic acid and oleic acid.

In one embodiment the polyester is derived from commercial12-hydroxy-stearic acid having a number average molecular weight ofabout 1600. Polyesters such as this are described in greater detail inU.K. Patent Specification Nos. 1373660 and 1342746.

In some embodiments the components used to prepare the additivesdescribed above are substantially free of, essentially free of, or evencompletely free of, non-polyester-containing hydrocarbyl substitutedacylating agents and/or non-polyester-containing hydrocarbyl substituteddiacylating agents, such as for example polyisobutylene succinicanhydride. In some embodiments these excluded agents are the reactionproduct of a long chain hydrocarbon, generally a polyolefin reacted witha monounsaturated carboxylic acid reactant, such as, (i)α,β-monounsaturated C₄ to C₁₀ dicarboxylic acid, such as, fumaric acid,itaconic acid, maleic acid.; (ii) derivatives of (i) such as anhydridesor C₁ to C₅ alcohol derived mono- or di-esters of (i); (iii)α,β-monounsaturated C₃ to C₁₀ monocarboxylic acid such as acrylic acidand methacrylic acid.; or (iv) derivatives of (iii), such as, C₁ to C₅alcohol derived esters of (iii) with any compound containing an olefinicbond represented by the general formula (R⁹)(R¹⁰)C═C(R¹¹)(CH(R⁷)(R⁸))wherein each of R⁹ and R¹⁰ is independently hydrogen or a hydrocarbonbased group; each of R¹¹, R⁷ and R⁸ is independently hydrogen or ahydrocarbon based group and preferably at least one is a hydrocarbylgroup containing at least 20 carbon atoms. In one embodiment, theexcluded hydrocarbyl-substituted acylating agent is a dicarboxylicacylating agent. In some of these embodiments, the excludedhydrocarbyl-substituted acylating agent is polyisobutylene succinicanhydride.

By substantially free of, it is meant that the components of the presentinvention are primarily composed of materials other than hydrocarbylsubstituted acylating agents described above such that these agents arenot significantly involved in the reaction and the compositions of theinvention do not contain significant amounts of additives derived fromsuch agents. In some embodiments the components of the invention, or thecompositions of the invention, may contain less than 10 percent byweight of these agents, or of the additives derived from these agents.In other embodiments the maximum allowable amount may be 5, 3, 2, 1 oreven 0.5 or 0.1 percent by weight. One of the purposes of theseembodiments is to allow the exclusion of agents such as polyisobutylenesuccinic anhydrides from the reactions of the invention and so, to alsoallow the exclusion of quaternized salt detergent additive derived fromagents such as polyisobutylene succinic anhydrides. The focus of thisinvention is on polyester, or hyperdispersant, quaternary salt detergentadditives.

b. The Quaternizing Agent

The quaternized salt detergents of the present invention are formed whenthe non-quaternized detergents described above are reacted with aquaternizing agent. Suitable quaternizing agents include selecteddialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates;hydrocarbyl epoxides in combination with an acid or mixtures thereof.

In one embodiment, the quaternizing agent can include alkyl halides,such as chlorides, iodides or bromides; alkyl sulphonates; dialkylsulphates, such as, dimethyl sulphate; sultones; alkyl phosphates; suchas, C1-12 trialkylphosphates; di C1-12 alkylphosphates; borates; C1-12alkyl borates; alkyl nitrites; alkyl nitrates; dialkyl carbonates; alkylalkanoates; O,O-di-C1-12 alkyldithiophosphates; or mixtures thereof.

In one embodiment, the quaternizing agent may be derived from dialkylsulphates such as dimethyl sulphate, N-oxides, sultones such as propaneand butane sultone; alkyl, acyl or araalkyl halides such as methyl andethyl chloride, bromide or iodide or benzyl chloride, and a hydrocarbyl(or alkyl) substituted carbonates. If the alkyl halide is benzylchloride, the aromatic ring is optionally further substituted with alkylor alkenyl groups.

The hydrocarbyl (or alkyl) groups of the hydrocarbyl substitutedcarbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atomsper group. In one embodiment, the hydrocarbyl substituted carbonatescontain two hydrocarbyl groups that may be the same or different.Examples of suitable hydrocarbyl substituted carbonates include dimethylor diethyl carbonate.

In another embodiment, the quaternizing agent can be a hydrocarbylepoxide, as represented by the following formula, in combination with anacid:

wherein R¹, R², R³ and R⁴ can be independently H or a hydrocarbyl groupcontain from 1 to 50 carbon atoms. Examples of hydrocarbyl epoxidesinclude: ethylene oxide, propylene oxide, butylene oxide, styrene oxideand combinations thereof. In one embodiment the quaternizing agent doesnot contain any styrene oxide.

In some embodiments the acid used with the hydrocarbyl epoxide may be aseparate component, such as acetic acid. In other embodiments, forexample when the hydrocarbyl acylating agent is a dicarboxylic acylatingagent, no separate acid component is needed. In such embodiments, thedetergent may be prepared by combining reactants which are essentiallyfree of, or even free of, a separate acid component, such as aceticacid, and rely on the acid group of the hydrocarbyl acylating agentinstead. In other embodiments, a small amount of an acid component maybe present, but at <0.2 or even <0.1 moles of acid per mole ofhydrocarbyl acylating agent. These acids may also be used with the otherquaternizing agents described above, including the hydrocarbylsubstituted carbonates and related materials described below.

In some embodiments the quaternizing agent of the invention does notcontain any substituent group that contains more than 20 carbon atoms.In other words, in some embodiments the long substituent group thatallows for the resulting additive to be organic soluble and thus usefulfor the purposes of this invention is not provided by the quaternizingagent but instead is brought to the additive by the non-quaternizeddetergents described above.

In certain embodiments the molar ratio of detergent having an aminefunctionality to quaternizing agent is 1:0.1 to 2, or 1:1 to 1.5, or 1:1to 1.3.

In another embodiment the quaternizing agent can be an ester of acarboxylic acid capable of reacting with a tertiary amine to form aquaternary ammonium salt, or an ester of a polycarboxylic acid. In ageneral sense such materials may be described as compounds having thestructure:

R¹⁹—C(═O)—O—R²⁰   (IX)

where R¹⁹ is an optionally substituted alkyl, alkenyl, aryl or alkylarylgroup and R²⁰ is a hydrocarbyl group containing from 1 to 22 carbonatoms.

Suitable compounds include esters of carboxylic acids having a pKa of3.5 or less. In some embodiments the compound is an ester of acarboxylic acid selected from a substituted aromatic carboxylic acid, ana-hydroxycarboxylic acid and a polycarboxylic acid. In some embodimentsthe compound is an ester of a substituted aromatic carboxylic acid andthus R¹⁹ is a subsituted aryl group. R may be a substituted aryl grouphaving 6 to 10 carbon atoms, a phenyl group, or a naphthyl group. R maybe suitably substituted with one or more groups selected fromcarboalkoxy, nitro, cyano, hydroxy, SR' or NR′R″ where each of R′ and R″may independently be hydrogen, or an optionally substituted alkyl,alkenyl, aryl or carboalkoxy groups. In some embodiments R′ and R″ areeach independently hydrogen or an optionally substituted alkyl groupcontaining from 1 to 22, 1 to 16, 1 to 10, or even 1 to 4 carbon atoms.

In some embodiments R¹⁹ in the formula above is an aryl groupsubstituted with one or more groups selected from hydroxyl, carboalkoxy,nitro, cyano and NH². R¹⁹ may be a poly-substituted aryl group, forexample trihydroxyphenyl, but may also be a mono-substituted aryl group,for example an ortho substituted aryl group. R¹⁹ may be substituted witha group selected from OH, NH₂, NO₂, or COOMe. Suitably R¹⁹ is a hydroxysubstituted aryl group. In some embodiments R¹⁹ is a 2-hydroxyphenylgroup. R²⁰ may be an alkyl or alkylaryl group, for example an alkyl oralkylaryl group containing from 1 to 16 carbon atoms, or from 1 to 10,or 1 to 8 carbon atoms. R²⁰ may be methyl, ethyl, propyl, butyl, pentyl,benzyl or an isomer thereof. In some embodiments R²° is benzyl ormethyl. In some embodiments the quaternizing agent is methyl salicylate.

In some embodiments the quaternizing agent is an ester of analpha-hydroxycarboxylic acid. Compounds of this type suitable for useherein are described in EP 1254889. Examples of suitable compounds whichcontain the residue of an alpha-hydroxycarboxylic acid include (i)methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, andallyl esters of 2-hydroxyisobutyric acid; (ii) methyl-, ethyl-, propyl-,butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of2-hydroxy-2-methylbutyric acid; (iii) methyl-, ethyl-, propyl-, butyl-,pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of2-hydroxy-2-ethylbutyric acid; (iv) methyl-, ethyl-, propyl-, butyl-,pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of lactic acid; and(v) methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, allyl-, benzyl-,and phenyl esters of glycolic acid. In some embodiments the quaternizingagent comprises methyl 2-hydroxyisobutyrate.

In some embodiments the quaternizing agent comprises an ester of apolycarboxylic acid. In this definition we mean to include dicarboxylicacids and carboxylic acids having more than 2 acidic moieties. In someembodiments the esters are alkyl esters with alkyl groups that containfrom 1 to 4 carbon atoms. Suitable example include diesters of oxalicacid, diesters of phthalic acid, diesters of maleic acid, diesters ofmalonic acid or diesters or triesters of citric acid.

In some embodiments the quaternizing agent is an ester of a carboxylicacid having a pKa of less than 3.5. In such embodiments in which thecompound includes more than one acid group, we mean to refer to thefirst dissociation constant. The quaternizing agent may be selected froman ester of a carboxylic acid selected from one or more of oxalic acid,phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid,nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.In some embodiments the quaternizing agent includes dimethyl oxalate,methyl 2-nitrobenzoate and methyl salicylate.

Any of the quaternizing agents described above, including thehydrocarbyl epoxides, may be used in combination with an acid. Suitableacids include carboxylic acids, such as acetic acid, propionic acid,2-ethylhexanoic acid, and the like.

Polyester Quaternized Detergent Containing Compositions

The quaternized salt detergents of the present invention may be used asan additive in various types of compositions, including fuelcompositions and additive concentrate compositions.

a. Fuel Compositions

The quaternized detergents of the present invention may be used as anadditive in fuel compositions. The fuel compositions of the presentinvention comprise the quaternized detergent additive described aboveand a liquid fuel, and is useful in fueling an internal combustionengine or an open flame burner. These compositions may also contain oneor more additional additives. These optional additives are describedbelow. In some embodiments, the fuels suitable for use in the presentinvention include any commercially available fuel, and in someembodiments any commercially available diesel fuel and/or biofuel.

The description that follows of the types of fuels suitable for use inthe present invention refer to the fuel that may be present in theadditive containing compositions of the present invention as well as thefuel and/or fuel additive concentrate compositions to which the additivecontaining compositions may be added.

Fuels suitable for use in the present invention are not overly limited.Generally, suitable fuels are normally liquid at ambient conditionse.g., room temperature (20 to 30° C.) or are normally liquid atoperating conditions. The fuel can be a hydrocarbon fuel,non-hydrocarbon fuel, or mixture thereof.

The hydrocarbon fuel can be a petroleum distillate, including a gasolineas defined by ASTM specification D4814, or a diesel fuel, as defined byASTM specification D975. In one embodiment the liquid fuel is agasoline, and in another embodiment the liquid fuel is a non-leadedgasoline. In another embodiment the liquid fuel is a diesel fuel. Thehydrocarbon fuel can be a hydrocarbon prepared by a gas to liquidprocess to include for example hydrocarbons prepared by a process suchas the Fischer-Tropsch process, and optionally hydro-isomerized. In someembodiments, the fuel used in the present invention is a diesel fuel, abiodiesel fuel, or combinations thereof.

Suitable fuels also include heavier fuel oils, such as number 5 andnumber 6 fuel oils, which are also referred to as residual fuel oils,heavy fuel oils, and/or furnace fuel oils. Such fuels may be used aloneor mixed with other, typically lighter, fuels to form mixtures withlower viscosities. Bunker fuels are also included, which are generallyused in marine engines. These types of fuels have high viscosities andmay be solids at ambient conditions, but are liquid when heated andsupplied to the engine or burner it is fueling.

The non-hydrocarbon fuel can be an oxygen containing composition, oftenreferred to as an oxygenate, which includes alcohols, ethers, ketones,esters of a carboxylic acids, nitroalkanes, or mixtures thereof.Non-hydrocarbon fuels can include methanol, ethanol, methyl t-butylether, methyl ethyl ketone, transesterified oils and/or fats from plantsand animals such as rapeseed methyl ester and soybean methyl ester, andnitromethane.

Mixtures of hydrocarbon and non-hydrocarbon fuels can include, forexample, gasoline and methanol and/or ethanol, diesel fuel and ethanol,and diesel fuel and a transesterified plant oil such as rapeseed methylester and other bio-derived fuels. In one embodiment the liquid fuel isan emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or amixture thereof.

In several embodiments of this invention the liquid fuel can have asulphur content on a weight basis that is 50,000 ppm or less, 5000 ppmor less, 1000 ppm or less, 350 ppm or less, 100 ppm or less, 50 ppm orless, or 15 ppm or less.

The liquid fuel of the invention is present in a fuel composition in amajor amount that is generally greater than 95% by weight, and in otherembodiments is present at greater than 97% by weight, greater than 99.5%by weight, greater than 99.9% by weight, or greater than 99.99% byweight.

b. Additive Concentrate Compositions

Additive concentrates are compositions that contain one or moreadditives and which may also contain some amount of fuel, oil, or adiluent of some type. These concentrates can then be added to othercompositions as a convenient way to handle and deliver the additives,resulting in the final compositions such as the fuel compositionsdescribed above.

The additive concentrate compositions of the present invention containone or more of the quaternized detergents described above and anoptional diluent, which may be any of the fuels described above, asolvent, a diluent oil, or similar material. These compositions may alsocontain one or more of the additional additives described below.

c. Optional Additional Additives

The compositions of the present invention include the quaternizeddetergents described above and may also include one or more additionaladditives. Such additional performance additives can be added to any ofthe compositions described depending on the results desired and theapplication in which the composition will be used.

Although any of the additional performance additives described hereincan be used in any of the compositions of the invention, the followingadditional additives are particularly useful for fuel compositions:antioxidants, corrosion inhibitors, detergent and/or dispersantadditives other than those described above, cold flow improvers, foaminhibitors, demulsifiers, lubricity agents, metal deactivators, valveseat recession additives, biocides, antistatic agents, deicers,fluidizers, combustion improvers, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors, or any combinationthereof.

Suitable antioxidants include for example hindered phenols orderivatives thereof and/or diarylamines or derivatives thereof. Suitabledetergent/dispersant additives include for example polyetheramines ornitrogen containing detergents, including but not limited to PIB aminedetergents/dispersants, succinimide detergents/dispersants, and otherquaternary salt detergents/dispersants includingpolyisobutylsuccinimide-derived quaternized PIB/amine and/or amidedispersants/detergents. Suitable cold flow improvers include for exampleesterified copolymers of maleic anhydride and styrene and/or copolymersof ethylene and vinyl acetate. Suitable demulsifiers include for examplepolyalkoxylated alcohols. Suitable lubricity agents include for examplefatty carboxylic acids. Suitable metal deactivators include for examplearomatic triazoles or derivatives thereof, including but not limited tobenzotriazole. Suitable valve seat recession additives include forexample alkali metal sulfosuccinate salts. Suitable foam inhibitorsand/or antifoams include for example organic silicones such aspolydimethyl siloxane, polyethylsiloxane, polydiethylsiloxane,polyacrylates and polymethacrylates, trimethyl-triflouropropylmethylsiloxane and the like. Suitable fluidizers include for example mineraloils and/or poly(alpha-olefins) and/or polyethers. Combustion improversinclude for example octane and cetane improvers.

The additional performance additives, which may be present in thecompositions of the invention, also include di-ester, di-amide,ester-amide, and ester-imide friction modifiers prepared by reacting adicarboxylic acid (such as tartaric acid) and/or a tricarboxylic acid(such as citric acid), with an amine and/or alcohol, optionally in thepresence of a known esterification catalyst. These friction modifiers,often derived from tartaric acid, citric acid, or derivatives thereof,may be derived from amines and/or alcohols that are branched, resultingin friction modifiers that themselves have significant amounts ofbranched hydrocarbyl groups present within it structure. Examples ofsuitable branched alcohols used to prepare such friction modifiersinclude 2-ethylhexanol, isotridecanol, Guerbet alcohols, and mixturesthereof.

The additional performance additives may comprise a high TBN nitrogencontaining detergent/dispersant, such as a succinimide, that is thecondensation product of a hydrocarbyl-substituted succinic anhydridewith a poly(alkyleneamine). Succinimide detergents/dispersants are morefully described in U.S. Pat. Nos. 4,234,435 and 3,172,892. Another classof ashless dispersant is high molecular weight esters, prepared byreaction of a hydrocarbyl acylating agent and a polyhydric aliphaticalcohol such as glycerol, pentaerythritol, or sorbitol. Such materialsare described in more detail in U.S. Pat. No. 3,381,022. Another classof ashless dispersant is Mannich bases. These are materials which areformed by the condensation of a higher molecular weight, alkylsubstituted phenol, an alkylene polyamine, and an aldehyde such asformaldehyde and are described in more detail in U.S. Pat. No.3,634,515. Other dispersants include polymeric dispersant additives,which are generally hydrocarbon-based polymers which contain polarfunctionality to impart dispersancy characteristics to the polymer. Anamine is typically employed in preparing the high TBNnitrogen-containing dispersant. One or more poly(alkyleneamine)s may beused, and these may comprise one or more poly(ethyleneamine)s having 3to 5 ethylene units and 4 to 6 nitrogen units. Such materials includetriethylenetetramine (TETA), tetraethylenepentamine (TEPA), andpentaethylenehexamine (PEHA). Such materials are typically commerciallyavailable as mixtures of various isomers containing a range number ofethylene units and nitrogen atoms, as well as a variety of isomericstructures, including various cyclic structures. The poly(alkyleneamine)may likewise comprise relatively higher molecular weight amines known inthe industry as ethylene amine still bottoms.

Dispersants can also be post-treated by reaction with any of a varietyof agents. Among these are urea, thiourea, dimercaptothiadiazoles,carbon disulfide, aldehydes, ketones, carboxylic acids,hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boroncompounds, and phosphorus compounds. References detailing such treatmentare listed in U.S. Pat. No. 4,654,403.

The compositions of the invention may include a detergent additive,different from the quaternized salt additive of the invention. Mostconventional detergents used in the field of engine lubrication obtainmost or all of their basicity or TBN from the presence of basicmetal-containing compounds (metal hydroxides, oxides, or carbonates,typically based on such metals as calcium, magnesium, or sodium). Suchmetallic overbased detergents, also referred to as overbased orsuperbased salts, are generally single phase, homogeneous Newtoniansystems characterized by a metal content in excess of that which wouldbe present for neutralization according to the stoichiometry of themetal and the particular acidic organic compound reacted with the metal.The overbased materials are typically prepared by reacting an acidicmaterial (typically an inorganic acid or lower carboxylic acid such ascarbon dioxide) with a mixture of an acidic organic compound (alsoreferred to as a substrate), a stoichiometric excess of a metal base,typically in a reaction medium of an one inert, organic solvent (e.g.,mineral oil, naphtha, toluene, xylene) for the acidic organic substrate.Typically also a small amount of promoter such as a phenol or alcohol ispresent, and in some cases a small amount of water. The acidic organicsubstrate will normally have a sufficient number of carbon atoms toprovide a degree of solubility in oil.

Such conventional overbased materials and their methods of preparationare well known to those skilled in the art. Patents describingtechniques for making basic metallic salts of sulfonic acids, carboxylicacids, phenols, phosphonic acids, and mixtures of any two or more ofthese include U.S. Pat. Nos. 2,501,731; 2,616,905; 2,616,911; 2,616,925;2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809;3,488,284; and 3,629,109. Salixarate detergents are described in U.S.Pat. No. 6,200,936.

Antioxidants encompass phenolic antioxidants, which may comprise a butylsubstituted phenol containing 2 or 3 t-butyl groups. The para positionmay also be occupied by a hydrocarbyl group or a group bridging twoaromatic rings. The latter antioxidants are described in greater detailin U.S. Pat. No. 6,559,105. Antioxidants also include aromatic amines,such as nonylated diphenylamine. Other antioxidants include sulfurizedolefins, titanium compounds, and molybdenum compounds. U.S. Pat. No.4,285,822, for instance, discloses lubricating oil compositionscontaining a molybdenum and sulfur containing composition. Typicalamounts of antioxidants will, of course, depend on the specificantioxidant and its individual effectiveness, but illustrative totalamounts can be 0.01 to 5, or 0.15 to 4.5, or 0.2 to 4 percent by weight.Additionally, more than one antioxidant may be present, and certaincombinations of these can be synergistic in their combined overalleffect.

Viscosity improvers (also sometimes referred to as viscosity indeximprovers or viscosity modifiers) may be included in the compositions ofthis invention. Viscosity improvers are usually polymers, includingpolyisobutenes, polymethacrylates (PMA) and polymethacrylic acid esters,hydrogenated diene polymers, polyalkylstyrenes, esterifiedstyrene-maleic anhydride copolymers, hydrogenatedalkenylarene-conjugated diene copolymers and polyolefins. PMA's areprepared from mixtures of methacrylate monomers having different alkylgroups. The alkyl groups may be either straight chain or branched chaingroups containing from 1 to 18 carbon atoms. Most PMA's are viscositymodifiers as well as pour point depressants.

Multifunctional viscosity improvers, which also have dispersant and/orantioxidancy properties are known and may optionally be used. Dispersantviscosity modifiers (DVM) are one example of such multifunctionaladditives. DVM are typically prepared by copolymerizing a small amountof a nitrogen-containing monomer with alkyl methacrylates, resulting inan additive with some combination of dispersancy, viscositymodification, pour point depressancy and dispersancy. Vinyl pyridine,N-vinyl pyrrolidone and N,N′-dimethylaminoethyl methacrylate areexamples of nitrogen-containing monomers. Polyacrylates obtained fromthe polymerization or copolymerization of one or more alkyl acrylatesalso are useful as viscosity modifiers.

Anti-wear agents can in some embodiments include phosphorus-containingantiwear/extreme pressure agents such as metal thiophosphates,phosphoric acid esters and salts thereof, phosphorus-containingcarboxylic acids, esters, ethers, and amides; and phosphites. In certainembodiments a phosphorus antiwear agent may be present in an amount todeliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08percent by weight phosphorus. Often the antiwear agent is a zincdialkyldithiophosphate (ZDP). For a typical ZDP, which may contain 11percent P (calculated on an oil free basis), suitable amounts mayinclude 0.09 to 0.82 percent by weight. Non-phosphorus-containinganti-wear agents include borate esters (including borated epoxides),dithiocarbamate compounds, molybdenum-containing compounds, andsulfurized olefins. In some embodiments the fuel compositions of theinvention are free of phosphorus-containing antiwear/extreme pressureagents.

Any of the additional performance additives described above may be addedto the compositions of the present invention. Each may be added directlyto the additive and/or the compositions of the present invention, butthey are generally mixed with the additive to form an additivecomposition, or concentrate, which is then mixed with fuel to result ina fuel composition. These various types of compositions are described inmore detail above. The amount of additional additives in the presentcomposition can typically be 1 to 10 weight percent, or 1.5 to 9.0percent, or 2.0 to 8.0 percent, all expressed on an oil-free basis.

The Process of Preparing the Quaternized Salt Detergent

The present invention provides a process of preparing quaternized amideand/or ester detergent where the process includes: reacting (a) apolyester containing a tertiary amino group; and (b) quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen, thereby obtaining the quaternized dispersant.

As described above the quaternizing agent may be selected from the groupconsisting of dialkyl sulfates, benzyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid or mixturesthereof.

The processes of the present invention may also be described as aprocess for preparing a quaternized detergent comprising the steps of:(1) mixing (a) a polyester containing a tertiary amino group, (b) aquaternizing agent and optionally (c) a protic solvent; (2) heating themixture to a temperature between 50° C. to 130° C.; and (3) holding forthe reaction to complete; thereby obtaining the quaternized detergent.In one embodiment the reaction is carried out at a temperature of lessthan 80° C., or less then 70° C. In other embodiments the reactionmixture is heated to a temperature of about 50° C. to 120° C., 80° C.,or 70° C. In still other embodiments the reaction temperature may be 70°C. to 130° C. In other embodiments the reaction temperature may be 50°C. to 80° C. or 50° C. to 70° C.

In some embodiments the processes of the present invention are free ofthe addition of any acid reactant, such as acetic acid. The salt productis obtained in these embodiments despite the absence of the separateacid reactant.

As described above, in some embodiments the non-quaternized polyestercontaining a tertiary amino group is the condensation product of a fattycarboxylic acid containing at least one hydroxyl group and a compoundhaving an oxygen or nitrogen atom capable of condensing with said acidand further having a tertiary amino group, thereby obtaining thepolyester containing a tertiary amino group. In some embodiments thecompound having an oxygen or nitrogen atom capable of condensing withsaid acid and further having a tertiary amino group is a diaminecontaining a tertiary amino group and a primary or secondary aminogroup.

The additives of the present invention may be derived in the presence ofa protic solvent. Suitable protic solvents include solvents that havedielectric constants of greater than 9. In one embodiment the proticsolvent includes compounds that contain 1 or more hydroxyl (—OH)functional groups, and may include water.

In one embodiment, the solvents are glycols and glycol ethers. Glycolscontaining from 2 to 12 carbon atoms, or from 4 to 10, or 6 to 8 carbonatoms, and oligomers thereof (e.g., dimers, trimers and tetramers) aregenerally suitable for use. Illustrative glycols include ethyleneglycol, propylene glycol, diethylene glycol, dipropylene glycol,1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, triethyleneglycol, polyethylene glycol and the like and oligomers and polymericderivative and mixtures thereof. Illustrative glycol ethers include theC₁-C₆ alkyl ethers of propylene glycol, ethylene glycol and oligomersthereof such as di-, tri- and tetra glycol ethers of methyl, ethyl,propyl, butyl or hexyl. Suitable glycol ethers include ethers ofdipropylene glycol, tripropylene glycol diethylene glycol, triethyleneglycol; ethyl diglycol ether, butyl diethyleneglycol ether,methoxytriethyleneglycol, ethoxytriethyleneglycol,butoxytriethyleneglycol, methoxytetraethyleneglycol,butoxytetraethyleneglycol.

Suitable solvents for use in the invention also include alcohols fromC1-20 including branched hydrocarbyl alcohols. Examples of suitablealcohols include 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol,2-ethylhexanol, 2-ethylnonanol, 2-propylheptanol, 2-butylheptanol,2-butyloctanol, isooctanol, dodecanol, cyclohexanol, methanol, ethanol,propan-1-ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol,butan-2-ol, pentanol and its isomers, and mixtures thereof. In oneembodiment the solvent of the present invention is 2-ethylhexanol,2-ethyl nonanol, 2-propylheptanol, or combinations thereof. In oneembodiment the solvent of the present invention includes 2-ethylhexanol.

The solvent can be any of the commercially available alcohols ormixtures of such alcohols and also includes such alcohols and mixturesof alcohols mixed with water. In some embodiments water is the onlysolvent used. In some embodiments the amount of water present may beabove 1 percent by weight of the solvent mixture. In other embodimentsthe solvent mixture may contain traces of water, with the water contentbeing less than 1 or 0.5 percent by weight.

The alcohols can be aliphatic, cycloaliphatic, aromatic, orheterocyclic, including aliphatic-substituted cycloaliphatic alcohols,aliphatic-substituted aromatic alcohols, aliphatic-substitutedheterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substitutedheterocyclic alcohols, heterocyclic-substituted aliphatic alcohols,heterocyclic-substituted cycloaliphatic alcohols, andheterocyclic-substituted aromatic alcohols.

While not wishing to be bound by theory, it is believed that a polarprotic solvent (which may include water) is required in order tofacilitate the dissociation of the acid into ions and protons. Thedissociation is required to protonate the ion formed when the detergenthaving an amine functionality initially reacts with the quaternizingagent. In the case where the quaternizing agent is an alkyl epoxide theresulting ion would be an unstable alkoxide ion. The dissociation alsoprovides a counter ion from the acid group of the additive that acts tostabilize the quaternary ammonium ion formed in the reaction, resultingin a more stable product.

INDUSTRIAL APPLICATION

In one embodiment, the process of the present invention produces aquaternized salt detergent. The quaternized detergent can be used as anadditive for use in a fuel for use in an internal combustion engineand/or an open flame burner.

The internal combustion engine includes spark ignition and compressionignition engines; 2-stroke or 4-stroke cycles; liquid fuel supplied viadirect injection, indirect injection, port injection and carburetor;common rail and unit injector systems; light (e.g. passenger car) andheavy duty (e.g. commercial truck) engines; and engines fuelled withhydrocarbon and non-hydrocarbon fuels and mixtures thereof. The enginesmay be part of integrated emissions systems incorporating such elementsas; EGR systems; aftertreatment including three-way catalyst, oxidationcatalyst, NOx absorbers and catalysts, catalyzed and non-catalyzedparticulate traps optionally employing fuel-borne catalyst; variablevalve timing; and injection timing and rate shaping.

The open flame burner burning may be any open-flame burning apparatusequipped to burn a liquid fuel. These include domestic, commercial andindustrial burners. The industrial burners include those requiringpreheating for proper handling and atomization of the fuel. Alsoincluded are oil fired combustion units, oil fired power plants, firedheaters and boilers, and boilers for use in ships and marineapplications including deep draft vessels. Included are boilers forpower plants, utility plants, and large stationary and marine engines.The open-flame fuel burning apparatus may be an incinerator such asrotary kiln incinerator, liquid injection kiln, fluidized bed kiln,cement kiln, and the like. Also included are steel and aluminum forgingfurnaces. The open-flame burning apparatus may be equipped with a fluegas recirculation system.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group. Asused herein, the term “hydrocarbonyl group” or “hydrocarbonylsubstituent” means a hydrocarbyl group containing a carbonyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

EXAMPLES

The invention will be further illustrated by the following examples.

While the Examples are provided to illustrate the invention, they arenot intended to limit it.

Example A Non-Quaternized Polyester Amide (Preparatory Material)

A non-quaternized polyester amide is prepared by reacting, in a jacketedreaction vessel fitted with stirrer, condenser, feed pump attached tosubline addition pipe, nitrogen line and thermocouple/temperaturecontroller system, 6 moles of 12-hydroxystearic acid and 1 mole ofdimethylaminopropylamine where the reaction is carried out at about 130°C. and held for about 4 hours. The reaction mixture is then cooled toabout 100° C. and zirconium butoxide is added, in an amount so that thecatalyst makes up 0.57 percent by weight of the reaction mixture. Thereaction mixture is heated to about 195° C. and held for about 12 hours.The resulting product is cooled and collected.

Example B Quaternized Polyester Amide Salt Detergent (Inventive Example)

A quaternized polyester amide salt detergent is prepared by reacting, ina jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system, 600 grams of thenon-quaternized polyester amide of Example A, 120 grams of2-ethylhexanol, 18.5 grams of acetic acid, and 32.3 ml of propyleneoxide, where the reaction is carried out at about 75° C. and thepropylene oxide is fed in to the reaction vessel over about 3.5 hours.The reaction mixture is then held at temperature for about 3 hours. 760grams of product is cooled and collected, which TAN, FTIR and ESI-MSanalysis confirms to be about 80% by weight quaternized polyester amidesalt detergent, with the remaining material being primarilynon-quaternized polyester amide. The collected material has a TAN of1.26 mg KOH/gram, a TBN of 23.82 mg KOH/gram, a kinematic viscosity at100° C. of 28.58 cSt (as measured by ASTM D445), an acetate peak by IRat 1574 cm⁻¹, and is 1.22% nitrogen.

Example C Non-Quaternized Polyester Amide (Preparatory Material)

A non-quaternized polyester amide is prepared by reacting, in a jacketedreaction vessel fitted with stirrer, condenser, feed pump attached tosubline addition pipe, nitrogen line and thermocouple/temperaturecontroller system, 1300 grams of ricinoleic acid and 73.5 grams ofdimethylaminopropylamine where the reaction is carried out at about 130°C., the amine is added dropwise over about 8 minutes, and the reactionmixture held for about 4 hours. The reaction mixture is then cooled toabout 100° C. and 7.8 grams of zirconium butoxide is added. The reactionmixture is heated to about 195° C. and held for about 17 hours. Theresulting product is filtered, cooled and collected. 1301 grams ofproduct is collected which has a TAN of 0 mg KOH/gram and shows by IR anester peak at 1732 cm⁻¹, an amide peak at 1654 cm⁻¹, but no acid peak at1700 cm⁻¹.

Example D Quaternized Polyester Amide Salt Detergent (Inventive Example)

A quaternized polyester amide salt detergent is prepared by reacting, ina jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system, 600 grams of thenon-quaternized polyester amide of Example C, 123 grams of2-ethylhexanol, 18.9 grams of acetic acid, and 33.1 ml of propyleneoxide, where the reaction is carried out at about 75° C. and thepropylene oxide is fed in to the reaction vessel over about 3.5 hours.The reaction mixture is then held at temperature for about 3 hours. 751grams of product is cooled and collected, which TAN, FTIR and ESI-MSanalysis confirms to be about 70% by weight quaternized polyester amidesalt detergent, with the remaining material being primarilynon-quaternized polyester amide. The collected material has a TAN of 0mg KOH/gram, a TBN of 23.14 mg KOH/gram, a kinematic viscosity at 100°C. of 47.0 cSt (as measured by ASTM D445), an acetate peak by IR at 1574cm⁻¹.

Example E Non-Quaternized Polyisobutylene Detergent (ComparativeExample)

A non-quaternized polyisobutylene monosuccinimide detergent is preparedby reacting, in a jacketed reaction vessel fitted with stirrer,condenser, feed pump attached to subline addition pipe, nitrogen lineand thermocouple/temperature controller system, 100 pbw polyisobutylenesuccinic anhydride (which is itself prepared from 1000 number averagemolecular weight high vinylidene polyisobutylene and maleic anhydridereaction in a 1:1.2 molar ratio) 13 pbw tetraethylenepentamine, wherethe anhydride is preheated to about 80° C., the amine is added to thesystem over about 8 hours, where the reaction mixture temperature iskept below 120° C. The reaction mixture is then heated to 170° C. andthen vacuum stripped. The resulting non-quaternized polyisobutylenemonosuccinimide detergent is cooled and collected.

Example F Quaternized Polyisobutylene Detergent (Comparative Example)

A quaternized polyisobutylene succinimide detergent is prepared byreacting, in a jacketed reaction vessel fitted with stirrer, condenser,feed pump attached to subline addition pipe, nitrogen line andthermocouple/temperature controller system, 100 pbw polyisobutylenesuccinic anhydride (which is itself prepared from 1000 number averagemolecular weight high vinylidene polyisobutylene and maleic anhydridereaction in a 1:1.2 molar ratio) 10.9 pbw dimethylaminopropylamine,where the anhydride is preheated to about 80° C., the amine is added tothe system over about 8 hours, where the reaction mixture temperature iskept below 120° C. The reaction mixture is then heated to 150° C. andheld for 3 hours, resulting in a non-quaternized polyisobutylenesuccinimide detergent. 40.6 pbw 2-ethylhexanol, 1 pbw water, 5.9 pbwacetic acid is then added to the non-quaternized polyisobutylenesuccinimide detergent. After a 3 hour hold 8.5 pbw propylene oxide isadded with the reaction being held at 75° C. for about 6 hours. Theresulting quaternized polyisobutylene succinimide detergent is cooledand collected.

XUD-9 Engine Testing

The Peugot XUD-9 engine in an indirect injection engine. In the test thepercent flow remaining in the fuel injector is measured at the end ofthe test, with higher percent flow remaining being desired, asindicative of reduced injector deposit formation. Separate XUD-9 enginetests were performed on a fuel composition containing Example B, a fuelcomposition containing Example F, and a fuel composition contain ExampleE. Each composition uses the same base fuel and contains 71 ppm of theadditive being evaluated. The base fuel is known to give a percentremaining flow of less than 20% when tested alone. The results obtainedare as follows:

TABLE 1 XUD-9 Engine Test Results Fuel Percent Flow Sample AdditiveEvaluated Remaining 1 Inventive Example B 84 2 Comparative Example F 1003 Comparative Example E 36

The results show that the Inventive Example B additive performs about aswell as the quaternized polyisobutylene succinimide detergent of ExampleF and much better than the non-quaternized polyisobutylene succinimidedetergent of Example E. All of the examples perform better than the basefuel alone, however the additives of Examples B and F performsignificantly better that the base fuel.

As discussed herein, the comparable XUD-9 engine test performancedelivered by Inventive Example B and Comparative Example F is importantwhen one then considers the superior viscosity and materials handlingproperties of Inventive Example B, further demonstrated below.

DW-10 Engine Testing

The DW-10 screen test uses the Coordinating European Council's (CEC)F-98-08 testing protocol, which utilizes a Peugeot DW-10 engine. This isa light duty direct injection, common rail engine test that measuresengine power loss, which relates to fuel detergent additive efficiency.Lower power loss values indicate better detergent performance. The testengine is representative of new engines coming into the market.

Each composition uses the same base fuel and contains 71 ppm, on anactives basis, of the additive being evaluated. The results obtained areas follows:

TABLE 2 DW-10 Engine Test Results Fuel Sample Additive Evaluated PercentPower Change at EOT 4 None - Base Fuel alone −5.1% 5 Inventive Example B+2.1% 6 Inventive Example D +1.1% 7 Comparative Example E −3.4% 8Comparative Example F +2.0%

The results show that the Inventive Example B and D additives performsabout as well as the quaternized polyisobutylene succinimide detergentof Example F and much better than the non-quaternized polyisobutylenesuccinimide detergent of Example E. All of the examples perform betterthan the base fuel alone, however the additives of Examples B, D and Fperform significantly better that the base fuel.

As discussed herein, the comparable DW-10 engine performance deliveredby Inventive Examples B, D and Comparative Example F is important whenone then considers the superior viscosity and materials handlingproperties of Inventive Examples B and D, further demonstrated below.

Viscometric & Materials Handling Properties

Material handling properties, which may be evaluated by considering thekinematic viscosity of a material, significantly impact how easily amaterial may be used in commercial products and/or the amount of diluentthat needs to be added to make the materials sufficiently handle-able,adding cost, complexity and waste to the overall process. Generallyspeaking, the lower the viscosity at 100° C. the better the materialhandling properties. For a proper comparison, the kinematic viscositiesof materials should be compared at an equal actives level, that is, withthe same amount of diluent oil and similar materials present.

To this end, Examples B, D and F were tested for viscosity at theiroriginal actives levels, about 85% actives for Example B and D, andabout 75% actives for Example F. Examples B and D were also tested forviscosity at 75% actives, all on a weight basis, to allow for a bettercomparison to Example F. The reduced actives samples are prepared bymixing the example additive with an appropriate amount of2-ethylhexanol. The viscosities of these blends were then determinedusing ASTM D445. The results obtained are presented below:

TABLE 3 Viscometric Data KV100 (cSt) KV100 (cSt) at about 85% actives atabout 75% actives Example (15% diluent) (25% diluent) B 79 23 D 47 39 F100

The results show that Inventive Examples B and D have a significantlylower kinematic viscosity at 100° C. compared to Comparative Example F,where the samples are considered at an actives level of 75%. Theseresults indicate that the Inventive Samples have significantly bettermaterial handling properties and could be more easily utilized in higherconcentrations without handling problems compared to the additives ofComparative Examples E and F.

Example G Quaternized Polyester Amide Salt Detergent (Inventive Example)

A quaternized polyester amide salt detergent is prepared by reacting, ina jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system, 3501 grams of thenon-quaternized polyester amide of Example A, 80.4 grams of acetic acid,24.5 grams of water, and 141.3 ml of propylene oxide, where the reactionis carried out at about 75° C. and the propylene oxide is fed in to thereaction vessel over about 4 hours with moderate stirring. The reactionmixture is then held at temperature for about 3 hours. 3710.5 grams ofproduct is cooled and collected, which TAN, FTIR and ESI-MS analysisconfirms to be >90% by weight quaternized polyester amide saltdetergent, with the remaining material being primarily non-quaternizedpolyester amide. The collected material has a TAN of 0 mg KOH/gram, aTBN of 27.76 mg KOH/gram, a kinematic viscosity at 100° C. of 327.4 cSt(as measured by ASTM D445), an acetate peak by IR at 1575 cm⁻¹, and is1.42% nitrogen.

Example H Quaternized Polyester Amide Salt Detergent (Inventive Example)

A quaternized polyester amide salt detergent is prepared by reacting, ina jacketed reaction vessel fitted with stirrer, condenser, feed pumpattached to subline addition pipe, nitrogen line andthermocouple/temperature controller system, 3401 grams of thenon-quaternized polyester amide of Example C, 107.3 grams of aceticacid, 32.0 grams of water, and 1875.1 ml of propylene oxide, where thereaction is carried out at about 75° C. and the propylene oxide is fedin to the reaction vessel over about 3.5 hours with moderate stirring.The reaction mixture is then held at temperature for about 3 hours.3687.8 grams of product is cooled and collected, which TAN, FTIR andESI-MS analysis confirms to be >90% by weight quaternized polyesteramide salt detergent, with the remaining material being primarilynon-quaternized polyester amide. The collected material has a TAN of 0mg KOH/gram, a TBN of 26.4 mg KOH/gram, a kinematic viscosity at 100° C.of 201.3 cSt (as measured by ASTM D445), an acetate peak by IR at 1574cm⁻¹, and is 1.33% nitrogen.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Except where otherwise indicated, all numerical quantities inthe description specifying amounts or ratios of materials are on aweight basis. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

What is claimed is:
 1. A composition comprising a quaternized polyestersalt which comprises the reaction product of: a. a polyester containinga tertiary amino group; and b. quaternizing agent suitable forconverting the tertiary amino group to a quaternary nitrogen.
 2. Thecomposition of claim 1 wherein the polyester comprises the reactionproduct of a fatty carboxylic acid containing at least one hydroxylgroup and a compound having an oxygen or nitrogen atom capable ofcondensing with said acid where said compound contains a tertiary aminogroup.
 3. The composition of claim 2 wherein the fatty carboxylic acidis represented by the formula:

where R¹ is a hydrogen or a hydrocarbyl group containing from 1 to 20carbon atoms and R² is a hydrocarbylene group containing from 1 to 20carbon atoms; and wherein the compound having an oxygen or nitrogen atomcapable of condensing with said acid and further having a tertiary aminogroup is represented by the formula:

where R³ is a hydrocarbyl group containing from 1 to 10 carbon atoms; R⁴is a hydrocarbyl group containing from 1 to 10 carbon atoms; R⁵ is ahydrocarbylene group containing from 1 to 20 carbon atoms; and X¹ is Oor NR⁶ where R⁶ is a hydrogen or a hydrocarbyl group containing from 1to 10 carbon atoms;
 4. The composition of claim 1 wherein thequaternized polyester salt comprises a quaternized polyester amide saltwherein the polyester containing a tertiary amino group used to preparesaid quaternized polyester salt comprises a polyester amide containing atertiary amino group.
 5. The composition of claim 1 wherein thequaternized polyester salt comprises a cation represented by thefollowing formula:

where R¹ is a hydrogen or a hydrocarbyl group containing from 1 to 20carbon atoms and R² is a hydrocarbylene group containing from 1 to 20carbon atoms; R³ is a hydrocarbyl group containing from 1 to 10 carbonatoms; R⁴ is a hydrocarbyl group containing from 1 to 10 carbon atoms;R⁵ is a hydrocarbylene group containing from 1 to 20 carbon atoms; R⁶ isa hydrogen or a hydrocarbyl group containing from 1 to 10 carbon atoms;n is a number from 1 to 10; R⁷ is hydrogen, a hydrocarbonyl groupcontaining from 1 to 22 carbon atoms, or a hydrocarbyl group containingfrom 1 to 22 carbon atoms; and X² is a group derived from thequaternizing agent.
 6. The composition of claim 2 wherein the compoundhaving an oxygen or nitrogen atom capable of condensing with said acidand further having a tertiary amino group comprisesN,N-diethylethylenediamine, N,N-dimethylethylenediamine,N,N-dibutylethylenediamine, N,N-dimethyl-1,3-diaminopropane,N,N-diethyl-1,3-diaminopropane, N,N-dimethylaminoethanol,N,N-diethylaminoethanol, or combinations thereof.
 7. The composition ofclaim 2 wherein the fatty carboxylic acid containing at least onehydroxyl group comprises: 12-hydroxystearic acid; ricinoleic acid;12-hydroxy dodecanoic acid; 5-hydroxy dodecanoic acid; 5-hydroxydecanoic acid; 4-hydroxy decanoic acid; 10-hydroxy undecanoic acid; orcombinations thereof.
 8. The composition of claim 1 wherein thequaternizing agent comprises ethylene oxide, propylene oxide, butyleneoxide, styrene oxide, or combinations thereof wherein the quaternizingagent is used in combination with an acid.
 9. The composition of claim 1further comprising a metal deactivator, a detergent other than those ofclaim 1, a dispersant, a viscosity modifier, a friction modifier, adispersant viscosity modifier, an extreme pressure agent, an antiwearagent, an antioxidant, a corrosion inhibitor, a foam inhibitor, ademulsifier, a pour point depressant, a seal swelling agent, a waxcontrol polymer, a scale inhibitor, a gas-hydrate inhibitor, orcombinations thereof.
 10. The composition of claim 1 further comprisingan overbased metal containing detergent, a zinc dialkyldithiophosphate,or combinations thereof.
 11. The composition of claim 1, furthercomprising a fuel which is liquid at room temperature.
 12. The method offueling an internal combustion engine comprising: A. supplying to saidengine: i. a fuel which is liquid at room temperature; and ii. acomposition comprising a quaternized polyester salt which comprises thereaction product of: (a) a polyester containing a tertiary amino group;and (b) quaternizing agent suitable for converting the tertiary aminogroup to a quaternary nitrogen.
 13. A process of making a quaternaryammonium salt detergent comprising: I. reacting (a) a polyestercontaining a tertiary amino group; and (b) quaternizing agent suitablefor converting the tertiary amino group to a quaternary nitrogen;thereby obtaining the quaternized dispersant.
 14. The process of claim14 wherein the polyester containing a tertiary amino group is preparedby a process comprising: I. reacting (a)(i) a fatty carboxylic acidcontaining at least one hydroxyl group and (a)(ii) a compound having anoxygen or nitrogen atom capable of condensing with said acid and furtherhaving a tertiary amino group; thereby obtaining the polyestercontaining a tertiary amino group.